Polyazo dyestuffs



Unitd Slams Patent POLYAZO DYES TUFFS Werner Bossard, Riehen, nearBase], and Marcel Reding, Basel, Switzerland, assignors to J. R. GeigyA.-G., Basel, Switzerland, a Swiss firm No Drawing. Application June 11,1 956 Serial No. 590,350

Claims priority, application Switzerland June27, 1955 7 Claims. cl,260-457) The invention is Concerned with substantive disazo and trisazodyestuffs, their production and their use forthe dyeing of cellulosematerial in fast, in particular very fast to light, yellow-orange,orange to yellow-brown shades.

It has been found that veryvaluable substantive disazo and trisazodyestuifs are obtained if an o-amino polyazo dyestuff of the generalFormula I which contains at least 2 and at most 5 sulphonic acid groups,is oxidised by methods known per se to form a 1.2.3-triazole compound ofthe general Formula ll Inthes'e formulae:

R represents an aromatic radical of the isocyclic or pound; also forexample it can represent the radical of a 2-(p-aminophenyl)-benzoor-naphthothiazole or triazole compound. In these compounds, the aromaticrings can be further substituted,e. g. with halogen, hydroxyl,

heterocyclic series which may possibly contain an arylazo group,preferably in the linkage,

R and Rg represent radicals of middle components usualin polyazodyestuffs which contain the 2120 groups prefera-bly in p-position toeach other in a benzene ring which may possibly form part ofa fused ringsystem,

R represents the radical of an azo component coupling in the o-positionto a primary amino group, and

R represents an aromatic radical bound by neighbouring carbon atoms tothe triazole ring.

p-position to the azo In these dyestuffs, R can represent the radical ofacarboxyl, alkyl, alkoxy and sulphonic acid groups as well as with theradicals of polynuclear compounds, e. g. with phenyl, benzyl or styrylgroups. They may also be fur ther substituted with arylazo groups andthe 4 latter can again be further substituted. In this substitution,arylazo' groups take preferably the p position to the 2120 group in abenzene ring linked to R which benzene ringcan form part of a fused ringsystem, e. g. a naphthalene, benztriazo'le or indazole ring. Thus R canbe derived for example from 1aminobenzene-3- or -4-sulphonic acid 01"carboxylic acid, 1-aminobenzene-2.4 or -2.5-disulphonic acid,4-chloro-l-aminobenzene-3-su1phonic acid, 4.6 dimethyl-I-aminoberizene-Z-sulphonic acid,5-amino"2-hydroxybenzenel-carboxylic acid and the corresponding3-sulphonic acid, 4-aminodiphenyl-3-sulphonic acid, 4- acet'ylamino4-aminodiphenyl-3-sulphonic acid, 4-n'itroor4-acylam'ino-4'-aminostilbene-2.2-disulphonic acids, 1aminonaphthalene-4-, -5-, -6- or -7-sulphonic acid, 2-ami=nonaphthalene-6- or -7-sulphonic acid, 2=aniinonaplrtha lene-3.6- or-5.7- or -4.8-disulphonic acid, l-arrtin'onaphthalene-3z6-"disulphonicacid, 3-amin'opyrene disulphonic acid, 2-(4-aminophenyl)-5-methylbenzthiazole mono and disulphonie acids,2-(4-aminophenyl)-naphthotriazole-5.7- disulphonic acid,2-(4'-aminophenyl)-naphthothiazole- 5,7-disulphonic acid,2-(4-aminophenyl)-naphthimidazole- 5.7-disulphonic acid,4-(naphthotriazolyl-2)-4-aminostilbene=2.2-disulphonic acid. R can alsobe derived from amino monoazo dyestuffs which are obtained by couplingone of the diazo components listed above with a middle component usualin polyazo dyestuffs coupling in the p position to a primary aminogroup, as is defined and illustrated in the following under R and R AlsoR can be derived from 4-arninoazobenzene and the monoand ldisulphonicacids thereof which can also be further substituted e. g. by methyl ormethoxy groups,

R and R are derived from the middle components usual in polyazodyestuffs, i. e. chiefly from primary amino compounds of the benzene,naphthalene and ucts according to the present invention if R is aradical of the benzene series.

All azo components of the benzene, naphthalene, anthracene andheterocyclic series coupling in o-position to a primary amino group canbe used as end components corresponding to R Examples are:1.3-diaminobenzene, 2.4-diamino-l -methylbenzene,2.4-diaminobenzene-l-sulphonic acid, 4 amino 2 methoxy l methylbenzene,5-amino-2-methoxy-l-methylbenzene, 1 aminonaphtha lene-4- and-5-sulphonic acid, preferably however, the 2-aminonaphthalene compoundscoupling in the l-position such as, e. g. Z-aminonaphthalene,Z-aminonaphthalene-lsulphonic acid, 2-aminonaphthalene-5-, -6- or-7-sulphonic acid, 2-aminonaphthalene-3.6- or -5.7-disulphonic acid,2-aminonaphthalene-3-carboxylic acid,2-amino-3-carboxynaphthalene-6-sulphonic acid,Z-arnino-S-hydroxynaphthalene-G-sulphonic acid,2-amino-S-hydroxynaphthalene-7-sulphonic acid, also 2-amino anthracene,S-aminobenztriazole, S-amino-2-phenylbenztriazole-3'- or -4'-sulphonicacid. It is of advantage for the properties of the dyestuffs accordingto the present invention to use end components which contain no furtheramino groups, apart from those which couple in the o-position to the azogroup, and which contain no aromatically bound hydroxyl group. In thisregard the 2-aminonaphthalene compounds coupling in the l-position areparticularly mentioned. In general, the polyazo dyestuffs according tothe present in ention are particularly valuable when they contain noaromatically bound amino and hydroxyl groups, i. e. if components areused for building up the dyestutf of the general Formula I which do notintroduce any such groups; also, in general, the disazo dyestuffsaccording to the present invention are more valuable than the trisazodyestuffs and are, therefore, to be preferred.

The o-amino polyazo dyestuffs of the general Formula I are oxidised toform the 1.2.3-triazole compounds of the general Formula II by methodsknown per se with oxidising agents which are capable of forming thetriazole ring in an alkaline solution. Cupritetrarnmine salts forexample can be used such as are obtained for example in aqueous solutionof the copper sulphate with excess ammonia or with excess organicamines, e. g. ethanolamines. Alkali hypochlorites can also be used asoxidising agents.

The oxidation is performed in aqueous solution, advan- SOIH tageously inthe warm, possibly while introducing air or oxygen. The completion ofthe oxidation is generally easily seen by a hypsochromic change ofcolour of the solution. The dyestuffs according to the present inven- Inthe form of their alkali salts, e. g. the lithium, sodium, potassium orammonium salts, the new disazo and trisazo dyestuffs according to theinvention are water soluble yellow-orange, orange to brown powders. Theydye cellulose material such as cotton and regenerated cellulose fibresfrom a dyebath containing Glaubers salt in orange to orange-brown shadeswhich are very fast to light.

The following examples illustrate the invention. Where not otherwisestated, parts are given as parts by weight. The temperatures are indegrees centigrade. The relationship of parts by weight to parts byvolume is as that of grammes to cubic centimetres.

EXAMPLE 1 54 parts of the amino disazo dyestuif obtained by couplingdiazotised Z-aminonaphthalene-4.8-disulphonic acid withl-amino-3-methlybenzene, further diazotisation of the aminomonoazodyestuff obtained and coupling with 1-amino-3-methylbenzene, aredissolved at with the addition of sodium carbonate so that the reactionis neutral. 7 parts of sodium nitrite are added and the mixture isdiazotised by the quick addition of 32 parts of hydrochloric acid atl0-l2. This diazonium compound is poured at 10 into a neutral solutionof 22.3 parts of Z-aminonaphthalene-G-sulphonic acid in 300 parts ofwater. The coupling is performed with a neutral reaction by thesimultaneous addition dropwise of sodium carbonate solution. Thecompletely formed amino trisazo dyestufi' is precipitated at 60 withsodium chloride, pasted in 1000 parts of water and heated to 98. Asolution of 50 parts of crystallised copper sulphate in 200 parts ofwater and 100 parts of 25% ammonia solution is added. After boiling forone hour, the violet red suspension changes to an orange colour. Theacidified dyestufl is filtered off, the filter cakes are dissolved withan alkaline reaction in 2000 parts of water and separated with sodiumchloride. The dyestuff obtained, when dry, is an orange-yellow powderwhich dissolves in water with an orange-yellow and in concentratedsulphuric acid with a blue colour. It dyes cotton a yellowish orangeshade and the dyeings have excellent fastness to light. The dyeings canbe discharged in a neutral and in an alkaline medium. The new dyestuff,as free acid, corresponds to the formula:

SOIH

If in the above example, the components given in the following table areused to form the aminotrisazo dyestulr' and the oxidation is performedby the method described or with parts of sodium hypochlorite solutionare precipitated with salt from the oxidation solu- 60 tion, whichcontains 18% active chlorine, then dyestuffs tions which are mostlyalkaline and then isolated.

are obtained which have similar properties.

Table Colour 1 No. Starting component (2)} component and component insubstance in water of cellulose dyeing 1 z-aminonaphthaicne-4.8-di- {(1)l-amino-e-mcthvlbenzene. z-aminonaphthalene-G-sulred yeiloworange.orange.

sulphonic acid. E2; l-amino-g-acetylaminoEenzene. phonic acid.

1 -amino- -ac t,v amino enzenc. 2 do Lammoaacetvaminobemene}2-aminonaphthalene red-brown .d0 Do. 3 2-amino'napl1thalene-6.8-dl-{(1) 1-amino-3-methylbenzene }2-arnin0naphthalene-B-sulyellow-brown.brown-yellow. yellowsulphonic acid. l-amino-g-mcmylgenzena phonic acid.orange.

-annno- -me y enzene. 4.--.-- .do mmmmgmethoxybemene }2-aminonaphtha1ene red brown...-- orange orange.

carcass 57.5 parts of the aminodisazo dyestulfl-aminonaphthalene-4-sulfonic acid- 1 aminonaphthalene 6 -sulphonicacid3 methy1-1-aminobenzene are diazotised by the method described inExample 1 and coupled with 22.3 parts of 2-aminonaphthalene-6-sulphonicacid to form the amino trisazo dyestufif. The completely formeddye'stufl? is precipitated from the alkaline solution with sodiumchloride and suspended in 1000 parts of water. It is then treated at araised temperature with 25 parts of sodiumhypochlorite 100% (as aqueoussolution) until the colour changes from violet to yellow-brown. Sodiumbicrabonate is added to the cooled dyestuff solution until itno longerhas a caustic alkaline reaction and the end dyestuff is precipitatedwith sodium chloride. After filtering off, the residue is washed free ofalkali with concentrated sodium chloride solution and dried. Thedyestutf is a brown-red powder which dissolves in water with anorange-brown and in concentrated sulphuric acid with a violet colour. Itdyes cellulose fibres in yellowish light.

Table -Continued Colour N dtarting component time component andcomponent I in substance in water of cellulose dyeing 5....-.fl-azninonaphthalene-4.8-di- {(1) l-amlnn-Z-methoxybemene.}l-am1nonnphthalene-3-sulyellow-brown. orange...- yellowsulphomc acid.(2) l-amlno-3-occtylamlnobenzcne phol to acid 5 orapge. 62-aniirlilonaphtliialene-ao-dii-gmino-gmckgylironzgncll-aglili)rilrglifiggtliill n brown 0 0. so p oncac r mmo- -mc y )enz 1e-s c (l) 1-an1ino-3-acetylaminobenzene. d 7 .-do -i {(2%)l-ainlno-Z-methoXy-E-methyk 2 i gfig g gg 6 Sn! n g gx cnzenc. 1 i (1)1am1no-3-methylbenzene 1 8 2-2g rfizg g22iigthm-5J-dl- H]mmo 2methoxyjmethy]: 2 gr ig ocn gpgthalene fisul do fin Do enzene. 1 9 d (1)1-arnino 3-rnethylbenzene }2-am1nonaphthalene-fieuldo do orange.

0 "Er"; "d' k2) ;-amlno-3-megyllgenzcne phonic acid. 10"-.. l-amlnonapthe ene-3.6- 1- 1) -aiuino-3-mo y enzone" sulphonic acid.1ggilarlig-bgigggilfiggngfigtfiglh do red "'T yellow brown gzg u dbenzene 5 2-arninonaphthalene-sulbrown orange yellow (2)bl-amiuni-methoxy-E-methyl phonic acid. bmwm cnzenc. 1 i 1)l-amlno-3-rnethylbenz1ie. LL 1 1 .12... 2-aminonaphtha1ene-4.8-di-Z-ammonaphthaIene-3fi-dired-brown -do yellow sulphonic acid. i g gg gf 2methoxy 5 methylp sulphonlc acid. orange. 13.--B-aminonaphthalene-6.8-di- (1) 1-arnlno-3-methylbenzenei u 1 sulphonicguild] 3 6 d1 11. m g gl w }5 aminobenztriazole brown yellow Do-arninona 1; aene- -arn1no- -rnc y cnzene. sulphonigacld. {(2)l-amino-B-methylbenzene. amlnobemthwmle Do l52-arn1n0nnphthalene-4.8-d1- {(1) 1-om no-3-mcthylbenzene}1-arn1no-3-hydroxybcnzeneyellow-brown. brown. sulphonic acid. l-amno-i-meiahylgenzene 1 icarboxylgc acidL.h 4 do yellow -um1no- -mc.1yenzone -amu1o -me oxy- 16 {(2) l-amino-3acctglar1inobenzeno.mcthylbenzene. orange. (1) l-arnluo-Ii-ruct y cnzene i r 17 ..d0 }1.3diamlnohtnzone yellow brown. do brown- 18 d (1)1'arnino-ti-mothylbenzene. }2-aminonaphtha1ene-7-sulred-brown orangeorange.

{(2) l-amino-li-mcthylbenzene. phonic acid. 19... dehydrothiotoluidinesul- (1) 1'Sullihacetylammo's'ammo' Z-ai-ninonaphthalene-fi-sulbrown doyellowh i d bonzem' honic acid orange. p on cam (2)1-amino-3-methylbenzenenui p f 20..- 2-arninonaphtha1ene-6.8-di- {(1)l-arnino-Ii-mcthylbenzene }2-ami11onaphtha1cne-7-sulyel1ow-brownyellow-brownyellowishsulphonic acid. (2) l-amino-3-methylbenzene phonicacid. I orange. '21.-.-L Z-aminonaphthaIenc-4.8-dl- {(1) l-aminohcnzene}2-am1nonophthalene-fi-sulred-brown... yellow-orangeyellowsulphonicacid. l-ami nnfimct-hylbonzene phonic acid. orange.

ammo rnzcnc... v 0 an 22.... .-do {(2)b0111122111120-.:-carhornrthoryammo- 2 ig gfifg ig 7 sul do r g (1)l-amirio-3-mcthylhenzenc. 1 a N 23 .-do {(2{)e1:.er:11ei,uo-3carbcthoxyamino- 2 ggg g gg 6 ml or EXAMPLE 2 50 brown shades which haveremarkable fastness to wet and -The free acid of the dyestuficorresponds to the formula:

If, instead of the combination 1-aminonaphtha1ene-4- sulphonic acid1-arninonaphthalene-o-sulphonic acid- 1- arnino-B methyibenzene- 2aminonaphthaiene 6 sulphonic acid, a combination given in the followingtable is oxidised with parts of sodium hypochlorite as in the aboveexample or with parts of copper sulphate and parts of 25% ammoniasolution, then dyestuffs with similar properties are obtained.

Table SC M- EC colour N0. Starting component middle component endcomponent in subin water of cellu stance lose dyeing 1 4-fiminpnzolcenzene 3.4 disul 1- amino 2 methoxy 5 1 aminonnphthalene 4sulbrown orange. yellow.

phonic acid. methylbcnzene. phonic acid. 2 4- 2111111104 -hydroxy-3-carboxy- Lamina-B-methylbenzcne. 2 aminonaphthalcne 6 sul -do do i..D0.

azobcnzeue-ii-sulphonic acid. phonic acid. 3. do 1 amino 3 acetylaminodo do do D0.

l V benzene. 4 4-annno-2-1nothy1 'if-hydroxy-w- --do2-ami11o-naphthalene do .do Do.

, carboxy azobenzene 5. sulphonic acid. 5 4-amino-2-methyl-5-methoxy-4'- 1-arnino-3-methylbenzene.. 2- aminonaphthalenc- 5 sui- Do.

hydroxy -3-carboxyazobenzenephonic acid. 5'-sulnhonic acid. 64.-aruino-3.2-dimethyiazobenzenedo 1 aminonaphthalene 3 sul- D- 5.44lisulphonic acid. phonic acid. 7..-.-." 4 amIlTOB-ZOhGHZGHQr- 3.4-disulr do l-arnino-ii-methoxy-A-methyl- D0.

phonic acid. benzene. 8; do dn 2 amino hydroxynapthared-brown...brownbrown. lcnc-7-sulphonic acid. orange. 9 v4-p-aminodrphenyl-4-hydroxy-3- 1-sulphacctylamino-3-ami- 2aminonaphthalene-o-sulbrown orange yellowcarboxyazobenzene. no-benzene.phonic acid. brown- EXAMPLE. 4

\ 5225iparts of the aminodisazodyestutf l aminobenzene-'4"-sulphonicacid' 1-aminonaphthalene-6-.sulphonic acid-e 5l-amino-Ii-rnethylbenzene in 800 parts of Water are diazoti'sed at 1012with7 parts of sodium nitrite and 32 partsof hydrochloric acidandcoupled in a weakly acid solution with 22.3 parts ofZi-aminonaphthalene-6-sulphonic acid. "The violet trisazo: dyestuflf isisolatediudisoff and washed with concentrated sodium chloride solution.it corresponds tothe forrnula:

SOaH

dyestuff are replaced by the equivalent number of parts solved in 1000parts of water and the reaction. is. made of theamino disazo-dyestulfslisted in the following table clearly alkaline with: 10 parts of 30%caustic soda l e. andthese are con led with the end components given ina a a y p n I I a The dyestuff solut1on is then treated at a raisedtemperathe table, then, after oxidizing. with a sodium hypochloture fonabout] hour with 25 parts of sodium hypochlorite solution (correspondingto 25 parts of 100% NaClO) rite 100% until the colour changes to andremains yellow 0f 19 0f crystallised pp Sulphate in P of brown. Sodiumbicarbonate is: added to. neutralise the water and; parts of 25% ammoniasolution, dyestufis excess caustic soda lye, the dyestufi is salted out,filtered [with similar properties are obtained.

Table SC- M M EC .1 l i (1) iddl colour l m e No. l Starting component(2)}component endcomponent in substance in water of celludlose yeingl-amggobenzene-4-sulphonic iaminonaaphthaiene-dgulphcnic acid lz-arlningnaphdthaleneo-sulbrown yellow-orange yellowac -arnino- -acetyamino enzene p on caci 1 orange. 2 do i-aminongaphEhalcneJ-gulphonicacid}1erginonaph1thalene-4-sui do do orange.

-arnino- -acc y am no cnzenc. p on each. 3--. 1-aminobenzene-2l5-disul-{(1) l-amino-a mcthylbenzene. }2-aminonaphthalcneG-sulred-brown".orangc.... yellow.

phonic acid. i-amino-g-mctgylgcnzenen phonic acid.

-amino- -mct y enzene 1 aminoig mothoxybenzene ammgnaphthalene V 5 {E3iifii g ii giii iiiiili eiiifii brow" 61-aminobenzene-3-sulphonl-aminogsulpfinacgtylaminobcnzcn}2=g.mii1%naphthalne-3.6- red-brown... do yellow. caci l-aniino- -rnct yenzene isu p ionic aci l l (1) 1-aminonaphthalene-(S-snlphonio aci2-amiuonaphthalene-5-suh brown do lied m 7 (2)1-amino-2-mcthoxy-S-mcthylbonzcne... phonic acid. ange 8.l-aming-2l4-girnethylibenl-amino-g-mrlztlylbinfene "B2ar1r]1inonapl:1tha1cnc-6-suldo yellow-orange. orange. zene- -su p onicaci 2 -amino- -su p ace y amino enzene p onic aci 9---l-aminobenzene-B-sulphon- {(1)1-amino-3-acetylaminobenzcne}1aminonaphthalene--suh do orange yellow-.-

' .1 icacid.3 b 4 h (2) l-amino-3-sulphacetylaminobonzcne -1 phonicacid. (1) l-arninobenzenc 2 arninona phthalone-3.6- .do yellow-orange.Do. g a Sulphon {(2) 1-amino-3-sulphacetylaminohenzene.. disulphonicacid. 11.... l-aminobenzene--sulphon- {(1) l-arnino-3-methylbenzene 1.}2-amino-5-hydroxynaphred-brown... orange yellowaci (2)1-amino-3-sulphacotylaminobenzene--. thalene-T-sulphonic acid. brown. 121aminobenzene-S-sulphon- {(1) 1-aznino-3-mcthylbcnzene}2-arnino-8-hydroxynaphdo do 1):).

lo acid; (2) l-amino-3-sulphacctylarninobenzenethalcnc-G-snlphonic acid.3 do {(1) l-amino-3-rncthylbenzene ..11-phcnyi-ii-methylfi-imibrown doyellow.

(2) 1-amino-3-snlphacctylaminohenzene- .y nopyrazoie. 14....l-an1lnobcnzene-2;5-d1sul {(1) lfimlllD-Z-mvihfixy5-1116171131051129116..}2-E1miflOllPlllhLhflltlIlU-5-SD1- rcd-br0wn... -..do orangephonicacid. (2) l-amino-3-acctylamlnobenzcne; phonic acid. red.

' l1 EXAMPLE 54 parts of the amino disazo dyestufiZ-aminonaphthalene-4.8-disulphonic acid 1-amino-3-methylbenzene- 1-amino-3-methylbenzene described in Example 1 are dissolved with aneutral reaction in 800 parts of water at 68 and diazotised at 0 with 7parts of sodium nitrite and 32 parts of hydrochloric acid. A weakly acidsolution of parts of 1-amino-3-acetyl-arninobenzene is added to thisdiazoniutn compound. On completion of the coupling, the

SOBH

precipitated dyestuff is filtered off, pasted in 600 parts of water anddiazotised at 0. The suspension of the diazonium compound is poured intoa solution of 22.3 parts of Z-aminonaphthalene-6-sulphonic acid in 300parts of water to which parts of sodium acetate have been added. Toaccelerate the coupling, sodium carbonate solution is addedsimultaneously until the reaction is neutral. The amino tetrakisazodyestuff is salted out at filtered off and suspended in 1000 parts ofwater and heated to After the addition of 50 parts of crystal- 10 Itsfree acid corresponds to the formula:

I NHCOCH:

The dyeings attained with this dyestuft' on cellulose fibers areyellow-brown and they are distinguished by good fastness to light. Theycan be discharged well.

If in the above example, the components used for forming the aminotetrakisazo dyestuff are altered according to the following table andthe dyestuffs obtained are oxidised by the method according to the mainexample or with a solution containing 25 parts of sodium hypochlorite inan alkaline medium, then dyestuffs with similar properties are obtained.

Table SC) My M3? M3") colour (1) N0. Starting component middlecomponent. end component of in substance in water cellulose dyeing 1"-amino-naphthalcne-4 8- (I) l'amir'o3'mmhylhenzme 1 aminonaphthalene 4red-brown orange ellowdisulmouic acid (2) l-illllln0-3lll(l.h)'lbfill20l'i0. l h i id 1 (3; l-amlno-ii-acetglmgi no-l cn no sup oncac l l-amino-B-mct ,vl cnzcne.. 2 do {(2) l-aminoB-acctylaminohonzr 'z fi ggg ig ggg 6 brown l-amino-g-ucctglaigiinobenzcne Il-amino-.-mct enzeno 3 z mgmg g g {(2) l-amino 3-mcthylhenzcnc2*aminonaphtha1cnc brown-red... do Do.

(3) l-aminoB-acctylnminobenz e. (1) l-aminonaphthalenc 6 sul 4 do phonicacid. Z-aminonaphthalcne 6 red-brown..- do brown.

"""""""" (2) l-amino-3-mcthylhenzcne. sulphouicacid.

(3) l-amino-3-acctylaminobenzcno..- 2 t l 57 (Dfi-nrninoniaphthalone 6sul- -am nonap acne p onic aci disulphonic acid. (2)i-amino-3-methylaminobenzene.. an do brown orange (3) I-amino-3-acctylitminobcnzcne. 6 1 hth 1 3 6 Laminobcnzcrge. .513.i

-ammonap acne i amino me y aminodisulphonic acid. benzene brow orange figw (3) l-aminn 3-mrthylbenzcne. (1) l-amino-Ii-mcthylbonzonc 7 do(2)1)l-amino-2-methoxy 3 methyl- 1 almhinonaphghalene 4 red-brown rinDc.

""""""""""""""""""" enzene. su p onic aci (3) l-amino-S-methylbenzcne(1) l-arninonaphthalene-G-sulphonic 8 1 aminobcnzene 4 sulacid. 2aminonaphthalene 6 brown-red.-. brown-orange. brown.

phonic acid. (2) 1-amino-3-methylhenzene sulphonic acid.

(3) l-amino-3-mothylbcnzene (I) 1aminonaphthalene-fi-sulphonic 9 1aminobenzcne 2.5 dl acid. 1 aminonaphthalene 3 brow do Do.

sulphonic acid. (2) l-amino-3-acctylaminobenzene..- sulphonic acid.

(3) l-amino-3-rncthylhcnzcnc I (l) l aminonaphthalcne 7 -su1- 10 i-anlnobenzene-S-sulphomc phonic acid. 2-aminonophthalene-3.6 brown-red"orange.-.--.-. Do.

ac (2) l-amino-3-acctylaminobenzone..- disulphonic acid.

(3) 1-amino-3-methylhcnzcnc (i) 161minonaphthalene-7-sulphonic aci u "do(2) 1 k; g-iigphthlaymlne-fi-sulphonic red-brown... orange-brown- Do.

y cnzene. (3) 1-arnino-3-acetylaminobcnzene... 1) 12 i b datrlijfiiggizgginimm isul {(2gmlidammonaphthalcne 6 sulphomczmaphthyhmme an 8 2 (113) l-amino-3-acel;ylaminohenzeueo 22253561125555ifi clmiilBali; l-amlnonaphtha1ene-4-sulbrow D0- 13 acidphonic acid .14 4 4 h 3 1-amino-3-methylbenzene-ammoyoroxycarboxyazohenzcne 3 {(2) l-aminonaphthalenc P z fi m gsulphonic acid. (3) l-amino-S-methylbenzcne lsu p omc am 1 154-am1no-2-methyl azobenz-ammonaphthalene-o-sulred-brow (in Do.

zene-2.5-disulph0nic acid. ilg g$gggig gk I: phonic acid.

13 EXAMPLE 6 A liquor is made from 1.0 part of the dyestuff obtainedaccording to Example 1 and 3 parts of sodium carbonate dissolved in 3000parts of water. 100 parts of cotton are entered at 40-50, the bath isheated within 30 minutes to,

The dyestuffs described in Examples 1--5 can be dyed in a similarmanner.

What we claim is: 1. A disazo dyestuif corresponding to the formulawherein R represents a member selected from the group consisting ofphenyl and naphthyl radicals, R represents an aromatic middle componentradical selected from the group consisting of phenylene and naphthyleneradicals, the -N=N- groups being in p-position to each other, Rrepresents a mononuclear carbocyclic middle component radical of thebenzene series, the bonds shown being in p-position to each other, m isan integer from 1 to 3 somgsncgjsgt inclusivej n is an integer from-0 to3 inclusilve arid p" is w an interger from 0 to 2 inclusive, the sum ofm and n being not more than 3 and the sum of m, n and p being at 1Iea'st-ZJand notmore'than 4.

2. A disazo dyestuff corresponding to the general formula:

wherein R represents a member selected from the group consisting of thephenyl and the naphthyl radical,

R represents an aromatic middle component :radical containing at leastone six-membered carbocyclic nucleus and at most two such nucleicondensed with one another, the -N=N- groups being in p-position to eachother,

X represents a member selected from the group consisting of -H, -CH--OCH and -NHacyl,

Y represents a member selected from the group consisting of --H, --CH-OCH m is one of the numerals 1 and 2,

n and p are each one of the numerals 0 and 1.

3. A disazo dyestutf corresponding to the formula:

SOIH

5. A disazo dyestufi corresponding to the formula:

SOIH

SOaH

6. A disazo dyestuif corresponding to the formula:

2,817,659 T5 16 7. 'A disazo'dyestufi' corresponding to the formula:

References Cited in the file of this patent UNITED STATES PATENTS2,268,935 Hanhart Jan. 6, 1942

1. A DISAZO DYESTUFF CORRESPONDING TO THE FORMULA